CN105513820B - A kind of preparation method of lithium manganese phosphate material of carbon coating and products thereof and application - Google Patents
A kind of preparation method of lithium manganese phosphate material of carbon coating and products thereof and application Download PDFInfo
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- CN105513820B CN105513820B CN201610017772.5A CN201610017772A CN105513820B CN 105513820 B CN105513820 B CN 105513820B CN 201610017772 A CN201610017772 A CN 201610017772A CN 105513820 B CN105513820 B CN 105513820B
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- lithium
- manganese phosphate
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- 239000000463 material Substances 0.000 title claims abstract description 125
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 27
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims abstract description 13
- 230000004044 response Effects 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000889 atomisation Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000012798 spherical particle Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 239000002105 nanoparticle Substances 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- DYWHBNOGMKFSKL-UHFFFAOYSA-M lithium ethane-1,2-diol acetate Chemical compound [Li+].CC([O-])=O.OCCO DYWHBNOGMKFSKL-UHFFFAOYSA-M 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 5 minutes Chemical compound 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000007441 Spherical agglomeration method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- MUXPMVYPHHPNHN-UHFFFAOYSA-N ethane-1,2-diol;manganese Chemical compound [Mn].OCCO MUXPMVYPHHPNHN-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- KEXXDMPEUZTTIS-UHFFFAOYSA-N ethane-1,2-diol;phosphoric acid Chemical compound OCCO.OP(O)(O)=O KEXXDMPEUZTTIS-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5805—Phosphides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
It is as follows the present invention relates to a kind of preparation method of the lithium manganese phosphate material of carbon coating：Lithium acetate is weighed respectively and protochloride manganese is dissolved in ethylene glycol, obtains clear solution I and clear solution II；Phosphoric acid is added dropwise in clear solution I, forms suspending liquid A；Clear solution II is added dropwise in suspending liquid A, obtains suspension B；Suspension B is subsequently transferred to heating response in reactor or glass three-neck flask, then post-treated acquisition nano manganese phosphate lithium material；Li, P, Mn mol ratio are 3.5~7 in described suspension B:1:1；By the nano manganese phosphate lithium material of preparation by carbon coating obtain 3~8 μm carbon coating lithium manganese phosphate material.The invention further relates to the lithium manganese phosphate material of carbon coating and its application, preparation method has easy to operate, and cost is low, and the advantages of can be mass-produced, resulting materials good dispersion, particle size is small, and high rate performance is good.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries, and in particular to a kind of preparation side of the lithium manganese phosphate material of carbon coating
Method and products thereof and application.
Background technology
In face of fossil energy and the increasingly serious situation of environmental pollution, new energy technology develops into today's society
Active demand.Lithium ion battery as green energy-storing application has high working voltage, and high-energy-density density is high, environment-friendly,
Have extended cycle life with security it is good the advantages of, it is consumer in notebook computer, mobile phone, camera, music player etc.
Field of batteries achieves significant development.
The positive electrode majority that consumer battery is used is LiCoO2, because its is expensive, have the shortcomings that toxicity not
It is suitable for the electrokinetic cell application field higher to energy density and security.Pure electric automobile and hybrid vehicle it is flourishing
Development, has driven the production of electrokinetic cell, while also the factors such as the energy density, security and cost of electrokinetic cell are proposed
Higher requirement.Olivine-type positive electrode LiFePO4Security it is good, cost is low, good cycle, meets electrokinetic cell
Requirement, but Shortcomings are gone back in energy density.It is all the LiMnPO of olivine-type4Current potential be 4.1V, compare LiFePO4's
Current potential 3.45V improves nearly 20%, and the raising for positive electrode energy density provides possibility.But lithium manganese phosphate positive pole material
In place of material still suffers from some shortcomings, such as electrical conductivity is low, ionic diffusion coefficient is low, bulk density is small, compacted density is low, causes it
Volume and capacity ratio is low, causes the preparation that can not also stablize at present.
The preparation method of lithium manganese phosphate is mainly solid phase method at present, by adulterating high conduction performance material and optimization material
Grain size can overcome the shortcomings of electric conductivity difference and cause material capacity low, such as Chinese patent (publication number CN104701535A)
A kind of preparation method of lithium manganese phosphate material is disclosed, and step is：Manganese sulfate crystal is dissolved in deionized water, then be added dropwise containing
Soluble phosphate and ammoniacal liquor, the mixed solution of surfactant, that is, obtain phosphoric acid Asia manganese；Certain ratio is added into phosphoric acid Asia manganese
The phosphoric acid solution of example, adds lithium carbonate, is then dried in vacuo solution, naturally cool to room temperature；By dried thing
Material takes out and is placed in mortar, adds lithium carbonate and glucose is fully ground, 700 DEG C are warming up to 5~10 DEG C/min of speed
Kept for 3 hours, then be warming up to 750 DEG C with 5 DEG C/min of speed and kept for 3 hours, then stopped heating, naturally cool to room temperature.In
State patent (publication number CN103050693A) discloses a kind of method for preparing spherical LiMnPO 4 anode material, including following step
Suddenly：Three kinds of Mn compound, P compound, Li compound raw materials are added in deionized water；Add dissolved organic carbon
Source；By gained mixed liquor by obtaining the mixed uniformly lithium manganese phosphate precursor powder of material after spray dryer spray pyrolysis；
2~3h is heated with 1~3kW.The manganese-lithium phosphate anode material appearance and size heterogeneity that the above method is prepared, has to performance
Large effect.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of preparation of the lithium manganese phosphate material of carbon coating
Method and products thereof and application, preparation method have easy to operate, and cost is low, the advantages of can be mass-produced, resulting materials point
Scattered property is good, and particle size is small, and high rate performance is good.
The present invention realizes that the technical scheme of purpose is：
A kind of preparation method of the lithium manganese phosphate material of carbon coating, comprises the following steps：
1) weigh lithium acetate and be dissolved in ethylene glycol, obtain clear solution I；Weigh protochloride manganese and be dissolved in ethylene glycol, obtain transparent
Solution II；
2) phosphoric acid is added dropwise in clear solution I, forms suspending liquid A；
3) clear solution II is added dropwise in suspending liquid A, obtains suspension B；Suspension B is subsequently transferred to reactor
Or heating response in glass three-neck flask, then post-treated acquisition nano manganese phosphate lithium material；Li, P in described suspension B,
Mn mol ratio is 3.5~7:1:1；
4) the nano manganese phosphate lithium material and organic carbon source of preparation are dispersed in water, 3~8 is obtained through atomization drying granulation
μm spherical particle, the lithium manganese phosphate material of carbon coating is obtained under inert atmosphere through high-temperature calcination.
The dropwise addition order of raw material of the present invention is lithium acetate, phosphoric acid and protochloride manganese.By the ratio for adjusting lithium acetate and phosphoric acid
Example, in higher non-stoichiometric, (Li and P mol ratio are 3.5~7:1) under, the small phosphoric acid of synthesis particle size is advantageous to
Lithium nucleus.The precursor solution added after protochloride manganese can obtain a nanometer phosphorus after reactor or the heating of glass three-neck flask
Sour manganese lithium material, the nano manganese phosphate lithium material that this method is prepared are made up of class fusiformis and spherical nano particle；Class shuttle
Shape nano particle length is in 50~150nm, and width is in 20~60nm；Spherical nanoparticle size size is in 20~50nm.Receive
Rice lithium manganese phosphate material can provide shorter passage for lithium ion transport, bigger with electrolyte contacts area, smaller body
Product change absolute value, therefore it is favorably improved the high rate performance and cycle performance of material.By the nano lithium manganese phosphate of lithium of synthesis with having
Machine carbon source is disperseed in a liquid, and atomization drying is granulated, and obtains the spherical agglomeration body of 3~8 μm of micron levels, meets industrialization pair
The requirement of lithium manganese phosphate material size.
Preferably, heating response reacts 8~12h under the conditions of 150~180 DEG C in described step 3).As entering one
Step is preferred, and heating response is reacted 9~10 hours under the conditions of 170~180 DEG C.Research is found, when reaction temperature is too low or reacts
Between shorten, the crystallinity and chemical property of material can be deteriorated.Too high reaction temperature and heat time, manganese element can be caused
Oxidation is so that thing is mutually impure, or material morphology change less causes the waste of energy consumption.
Preferably, described phosphoric acid concentration is not less than 85wt%.The step of preparing phosphoric acid ethylene glycol solution is omitted, is simplified
Technological process.
Preferably, in described step 1), the concentration of lithium acetate is 0.5~4.2mol/L in clear solution I, transparent molten
The concentration of protochloride manganese is 0.2~0.6mol/L in liquid II.As further preferred, in described step 1), in clear solution I
The concentration of lithium acetate is 2~2.5mol/L, and the concentration of protochloride manganese is 0.4~0.5mol/L in clear solution II.
Preferably, post processing refers to wash using deionized water and absolute ethyl alcohol in described step 3), it is with rotating speed
8000rpm~12000rpm centrifuge is centrifuged, and is dried at 60~100 DEG C and is obtained dry nano lithium manganese phosphate of lithium material
Material.
Preferably, the organic carbon source in described step 4) is selected from glucose, sucrose, starch, polyvinylpyrrolidone
(PVP), the one or more in vitamin C, citric acid.
Preferably, the feed end temperature of atomization drying is 190~240 DEG C in described step 4), collection material end
Temperature is 100~130 DEG C, and atomization rates are 5~20ml/min.
Preferably, the calcining heat of described step 4) high temperature calcining is 500~700 DEG C, calcination time is 3~
6h。
Preferably, suspension B is transferred to heating response in reactor in described step 3), in described suspension B
Li, P, Mn mol ratio are 4.5~5.5:1:1.First, Li, P, Mn mol ratio are too low or too high can generate dephasign.Its
It is secondary, under the molar ratio of Li, P, the Mn, and heating response in a kettle, the nano manganese phosphate lithium material of gained by
Class fusiformis and spherical nano particle composition；Class fusiformis nano particle length is in 50~150nm, and width is in 20~60nm；Class ball
Shape nanoparticle size size is in 20~50nm.Nano manganese phosphate lithium material because of its less size and larger specific surface area,
Therefore smaller lithium ion and electric transmission distance, the contact area and less body of bigger electrode and electrolyte can be realized
Product change absolute value, could so cause the capacity and high rate performance of lithium ion battery, and cycle performance can be improved.Then
Disperse in a liquid with organic carbon source, atomization drying is granulated, and obtains the spherical agglomeration body of micron level, meets industrialization to phosphorus
The requirement of sour manganese lithium material size, the lithium manganese phosphate material even particle distribution of the carbon coating of gained, chemical property are good.
The present invention also provides a kind of lithium manganese phosphate material of carbon coating, the size of the lithium manganese phosphate material of described carbon coating
Size is 4~6 μm, and the lithium manganese phosphate material of carbon coating is made up of nano manganese phosphate lithium material with carbon；Described nano manganese phosphate
Lithium material is made up of class fusiformis and spherical nano particle；Class fusiformis nano particle length in 50~150nm, width 20~
60nm；Spherical nanoparticle size size is in 20~50nm.
The present invention also provides a kind of lithium manganese phosphate material of carbon coating in anode material for lithium-ion batteries or lithium ion super
Application in capacitor.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) present invention is granulated using liquid phase method and atomization drying and is prepared lithium manganese phosphate material, has easy to operate, cost
The advantages that low, suitable large-scale production.
(2) the nano manganese phosphate lithium material primary particle for preparing of the present invention is class fusiformis and spherical nano particle, carbon
It is the spherical aggregate of micron that cladding, which obtains second particle, is advantageous to reduce intercalation/deintercalation distance, increase and the electrolyte of lithium ion
Infiltration, the raising to the special high rate performance of chemical property of material is of great advantage.
(3) lithium manganese phosphate material of carbon coating structural stability in charge and discharge process is good, has higher stable circulation
Property, available for anode material for lithium-ion batteries or ultracapacitor.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of nano manganese phosphate lithium material prepared by embodiment 1；
Fig. 2 is ESEM (SEM) figure of nano manganese phosphate lithium material prepared by embodiment 1；
Fig. 3 is ESEM (SEM) figure before the lithium manganese phosphate material calcination processing of carbon coating prepared by embodiment 1；
Fig. 4 is ESEM (SEM) figure after the lithium manganese phosphate material calcination processing of carbon coating prepared by embodiment 1
Fig. 5 is transmission electron microscope (TEM) figure of the lithium manganese phosphate material of carbon coating prepared by embodiment 1；
Fig. 6 be respectively using embodiment 1 (S-1) and comparative example 2 (S-2) preparation carbon coating lithium manganese phosphate material as lithium from
The cycle performance figure that the button cell of sub- cell positive material assembling is carried out；
Fig. 7 be respectively using embodiment 1 (S-1) and comparative example 2 (S-2) preparation carbon coating lithium manganese phosphate material as lithium from
The high rate performance figure that the button cell of sub- cell positive material assembling is carried out；
Fig. 8 is ESEM (SEM) figure of nano manganese phosphate lithium material prepared by comparative example 1.
Embodiment
Embodiment 1
1st, nano manganese phosphate lithium material is prepared
The lithium acetate for weighing 6.1213g (0.06mol) is dissolved in 30ml ethylene glycol, and magnetic agitation adds ultrasound 10 minutes extremely
Solution is transparent, obtains the lithium acetate ethylene glycol clear solution I that molar concentration is 2mol/L；Weigh 2.3988g's (0.012mol)
Protochloride manganese is dissolved in 30ml ethylene glycol, 5 minutes, chlorine that acquisition molar concentration be 0.4mol/L transparent to solution of magnetic agitation
Change sub- manganese ethylene glycol clear solution II；820 μ L pure phosphoric acid is measured with pipette, is added dropwise in clear solution I, side is added dropwise
Side is stirred, and forms white suspension A.Clear solution II is then slowly added dropwise in suspending liquid A, after being added dropwise, stirs 10 points
The bell suspension B into baby pink.Li, P, Mn ratio are 5 in suspension B:1:1.It is poly- that suspension B is transferred into liner
In tetrafluoroethene reactor, liner volume is 100ml.Then reactor is placed in convection oven, it is small that 10 are incubated at 180 DEG C
When.Room temperature taking-up is naturally cooled to, is centrifuged respectively three times using deionized water, absolute ethyl alcohol, the rotating speed of centrifuge is
10000rpm.The sediment obtained after centrifugation is placed in 80 DEG C of baking oven, drying time is 12 hours.It is polished after drying
Obtain nano manganese phosphate lithium material.X-ray diffraction is carried out to the nano manganese phosphate lithium material of gained and ESEM characterizes,
As depicted in figs. 1 and 2.Wherein X ray diffracting spectrum is corresponding with standard spectrum, it was demonstrated that material structure is olivine-type lithium manganese phosphate
Phase.By ESEM Fig. 2, in class fusiformis and spherical, class fusiformis particle length exists prepared material primary particle
50~150 nanometers, width is at 20~60 nanometers；Spherical particle size is at 20~50 nanometers.
2nd, the lithium manganese phosphate material of carbon coating is prepared
By nano manganese phosphate lithium material, sucrose and polyvinylpyrrolidone (PVP) using mass ratio as 1:0.25:1 is dispersed in
In deionized water, stir, wherein solid content is 20%.Through being atomized drying and processing, the spherical carbon coating of micron is obtained
Lithium manganese phosphate material.Atomization rates are 5ml/min, and drying condition is that inlet temperature is 220 DEG C, and discharging opening temperature is 120
℃.The powder that discharging opening is obtained is placed in tube furnace, passes to argon gas atmosphere, is reached from room temperature with 5 DEG C/min heating rate
600 DEG C, calcine 4 hours, naturally cool to room temperature.Tested by carbon content, the carbon content in the compound is about 10wt%.It is right
The lithium manganese phosphate material of carbon coating before and after calcination processing is scanned Electronic Speculum, as shown in Figure 3 and Figure 4, secondary as can be known from Figure
Particle is the spherical agglomerates with fold of the microns of size 5, and material morphology can be maintained after calcining；To carbon coating
Lithium manganese phosphate material carry out transmission electron microscope, as shown in Figure 5.
3rd, performance test
Material assembling button cell is subjected to electrochemical property test, voltage tester scope is 2.0~4.5V, current density
1C=170mA/g.Shown in the cycle performance of resulting materials such as Fig. 6 (curve S-1).Capacity when material circulation number is 1 is
132.9mA h g-1, capacity when cycle-index is 200 is 95.3mA h g-1, show higher capacity and stable circulation
Property.Shown in the high rate performance of resulting materials such as Fig. 7 (curve S-1), performance is equally more satisfactory, under 10C current density, holds
Amount also has close to 90mAh g-1。
Embodiment 2
1st, nano manganese phosphate lithium material is prepared
The lithium acetate for weighing 6.1213g (0.06mol) is dissolved in 30ml ethylene glycol, and magnetic agitation adds ultrasound 10 minutes extremely
Solution is transparent, obtains the lithium acetate ethylene glycol clear solution I that molar concentration is 2mol/L；Weigh 2.9985g's (0.015mol)
Protochloride manganese is dissolved in 30ml ethylene glycol, 5 minutes, chlorine that acquisition molar concentration be 0.5mol/L transparent to solution of magnetic agitation
Change sub- manganese ethylene glycol clear solution II；1025 μ L pure phosphoric acid is measured with pipette, is added dropwise in clear solution I, side drop
Edged stirs, and forms white suspension A.Clear solution II is then slowly added dropwise in suspending liquid A, after being added dropwise, stirring 10
Minute forms the suspension B of baby pink.Li, P, Mn ratio are 4 in suspension B:1:1.Suspension B is transferred into liner is
In ptfe autoclave, liner volume is 100ml.Then reactor is placed in convection oven, it is small that 9 are incubated at 170 DEG C
When.Room temperature taking-up is naturally cooled to, is centrifuged respectively three times using deionized water, absolute ethyl alcohol, the rotating speed of centrifuge is
10000rpm.The sediment obtained after centrifugation is placed in 80 DEG C of baking oven, drying time is 12 hours.It is polished after drying
Obtain nano manganese phosphate lithium material.
2nd, the lithium manganese phosphate material of carbon coating is prepared
By nano manganese phosphate lithium material, sucrose and polyvinylpyrrolidone (PVP) using mass ratio as 1:0.25:1 is dispersed in
In deionized water, stir, wherein solid content is 20%.Through being atomized drying and processing, the spherical lithium manganese phosphate of micron is obtained
Material.Atomization rates are 5ml/min, and drying condition is that inlet temperature is 220 DEG C, and discharging opening temperature is 120 DEG C.By discharging opening
Obtained powder is placed in tube furnace, passes to argon gas atmosphere, reaches 600 DEG C from room temperature with 5 DEG C/min heating rate, insulation 4
Hour, naturally cool to room temperature.Tested by carbon content, the carbon content in the compound is about 10wt%.
By ESEM and transmission electron microscope picture, prepared material primary particle is in class fusiformis and spherical, class
Fusiformis particle length is at 50~150 nanometers, and width is at 20~60 nanometers；Spherical particle size is at 20~50 nanometers.Two
Secondary particle is the spherical agglomerates with fold of the microns of size 5, and material morphology can be maintained after calcining.
3rd, performance test
Material assembling button cell is subjected to electrochemical property test, voltage tester scope is 2.0~4.5V, current density
1C=170mA/g.Capacity when material circulation number is 1 is 122.6mA h g-1, capacity when cycle-index is 200 is
87.4mA h g-1, show higher capacity and cyclical stability.The high rate performance of material is equally more satisfactory, in 10C electricity
Under current density, capacity also has 75.1mA h g-1。
Embodiment 3
1st, nano manganese phosphate lithium material is prepared
The lithium acetate for weighing 7.3456g (0.072mol) is dissolved in 30ml ethylene glycol, and magnetic agitation adds ultrasound 10 minutes
It is transparent to solution, obtain the lithium acetate ethylene glycol clear solution I that molar concentration is 2.4mol/L；Weigh 2.3988g
The protochloride manganese of (0.012mol) is dissolved in 30ml ethylene glycol, and magnetic agitation 5 minutes is transparent to solution, is obtained molar concentration and is
0.4mol/L protochloride manganese ethylene glycol clear solution II；820 μ L pure phosphoric acid is measured with pipette, is added dropwise to transparent molten
In liquid I, stirred when being added dropwise, form white suspension A.Clear solution II is then slowly added dropwise in suspending liquid A, is added dropwise
Afterwards, 10 minutes suspension B for forming baby pink are stirred.Li, P, Mn ratio are 6 in suspension B:1:1.Suspension B is turned
Liner is moved on to as in ptfe autoclave, liner volume is 100ml.Then reactor is placed in convection oven, 175 DEG C
Lower insulation 9.5 hours.Room temperature taking-up is naturally cooled to, is centrifuged respectively three times using deionized water, absolute ethyl alcohol, centrifuge turns
Speed is 10000rpm.The sediment obtained after centrifugation is placed in 80 DEG C of baking oven, drying time is 12 hours.Through grinding after drying
Nano manganese phosphate lithium material is obtained after mill.
2nd, the lithium manganese phosphate material of carbon coating is prepared
By nano manganese phosphate lithium material, sucrose and polyvinylpyrrolidone (PVP) using mass ratio as 1:0.25:1 is dispersed in
In deionized water, stir, wherein solid content is 20%.Through being atomized drying and processing, the spherical lithium manganese phosphate of micron is obtained
Material.Atomization rates are 5ml/min, and drying condition is that inlet temperature is 220 DEG C, and discharging opening temperature is 120 DEG C.By discharging opening
Obtained powder is placed in tube furnace, passes to argon gas atmosphere, reaches 600 DEG C from room temperature with 5 DEG C/min heating rate, insulation 4
Hour, naturally cool to room temperature.Tested by carbon content, the carbon content in the compound is about 10wt%.
By ESEM and transmission electron microscope picture, prepared material primary particle is in class fusiformis and spherical, class
Fusiformis particle length is at 50~150 nanometers, and width is at 20~60 nanometers；Spherical particle size is at 20~50 nanometers.Two
Secondary particle is the spherical agglomerates with fold of the microns of size 5, and material morphology can be maintained after calcining.
3rd, performance test
Material assembling button cell is subjected to electrochemical property test, voltage tester scope is 2.0~4.5V, current density
1C=170mA/g.Capacity when material circulation number is 1 is 115.9mA h g-1, capacity when cycle-index is 200 is
104.5mA h g-1, show higher capacity and cyclical stability.The high rate performance of material is equally more satisfactory, 10C's
Under current density, capacity also has 89.7mA h g-1。
Comparative example 1
1st, nano manganese phosphate lithium material is prepared
The lithium acetate for weighing 2.4485g (0.024mol) is dissolved in 30ml ethylene glycol, and magnetic agitation adds ultrasound 10 minutes
It is transparent to solution, obtain the lithium acetate ethylene glycol clear solution I that molar concentration is 0.8mol/L；Weigh 2.3988g
The protochloride manganese of (0.012mol) is dissolved in 30ml ethylene glycol, and magnetic agitation 5 minutes is transparent to solution, is obtained molar concentration and is
0.4mol/L protochloride manganese ethylene glycol clear solution II；820 μ L pure phosphoric acid is measured with pipette, is added dropwise to transparent molten
In liquid I, stirred when being added dropwise, form white suspension A.Clear solution II is then slowly added dropwise in suspending liquid A, is added dropwise
Afterwards, 10 minutes suspension B for forming baby pink are stirred.Li, P, Mn ratio are 2 in suspension B:1:1.Suspension B is turned
Liner is moved on to as in ptfe autoclave, liner volume is 100ml.Then reactor is placed in convection oven, 180 DEG C
Lower insulation 10 hours.Room temperature taking-up is naturally cooled to, is centrifuged respectively three times using deionized water, absolute ethyl alcohol, centrifuge turns
Speed is 10000rpm.The sediment obtained after centrifugation is placed in 80 DEG C of baking oven, drying time is 12 hours.
The X ray diffracting spectrum of resulting materials shows that dephasign occurs in material, wherein containing LiMnPO4And Mn7(PO3OH)4
(PO4)2Two-phase, but material is changed into LiMnPO after the calcining of bag carbon high-temp4Pure phase.From Fig. 8 scanning electron microscope diagram
It can be seen that material is in random big thin slice pattern.The length of material and wide in 1 microns, thickness about 20nm, through grinding after drying
Nano manganese phosphate lithium material is obtained after mill.
2nd, the lithium manganese phosphate material of carbon coating is prepared
By nano manganese phosphate lithium material, sucrose and polyvinylpyrrolidone (PVP) using mass ratio as 1:0.25:1 mixing, puts
In tube furnace, argon gas atmosphere is passed to, 600 DEG C is reached from room temperature with 5 DEG C/min heating rate, is incubated 4 hours, natural cooling
To room temperature.To be tested by carbon content, the carbon content in the compound is about 10wt%,.Material assembling button cell is subjected to electricity
Chemical property is tested, and voltage tester scope is 2.0~4.5V, current density 1C=170mA/g.Electro-chemical test is carried out to material
Understand, the performance of material is far below the chemical property of embodiment 1.In 0.05C constant current charge-discharges, material circulation number is
Capacity when 5 only has 40mA h g-1.As can be seen here, the lithium acetate in preparation process in presoma, phosphoric acid and protochloride manganese
Ratio has significant impact for the pattern and chemical property of material.
Comparative example 2
Using suspension B same as Example 1, it is transferred in 500ml three-neck flask, passes to nitrogen protection atmosphere,
And cooling and reflux device is installed.Reacted 2 hours at 140 DEG C, other steps are identical.Pure phase can be prepared by this method
Lithium manganese phosphate, the microscopic appearance of material is nano particle, and size is at 20~50 nanometers.
Similar bag carbon and electro-chemical test are carried out to material.Voltage tester scope is 2.0~4.5V, current density 1C=
170mA/g.Shown in the cycle performance of resulting materials such as Fig. 6 (curve S-2).Capacity when material circulation number is 1 is
85.6mA h g-1, capacity when cycle-index is 200 is 85.2mA hg-1, far below the chemical property of the material of embodiment 1.
Shown in the high rate performance of resulting materials such as Fig. 6 (curve S-2), under 10C current density, capacity only has 45.8mA h g-1.By
This is visible, and the material synthesized under low temperature and condition of normal pressure is unfavorable for the release of material electrochemical performance.
Claims (7)
1. a kind of preparation method of the lithium manganese phosphate material of carbon coating, it is characterised in that comprise the following steps：
1) weigh lithium acetate and be dissolved in ethylene glycol, obtain clear solution I；Weigh protochloride manganese and be dissolved in ethylene glycol, obtain clear solution
Ⅱ；
2) phosphoric acid is added dropwise in clear solution I, forms suspending liquid A；
3) clear solution II is added dropwise in suspending liquid A, obtains suspension B；Suspension B is subsequently transferred to reactor or glass
Heating response in glass three-neck flask, then post-treated acquisition nano manganese phosphate lithium material；Li, P, Mn in described suspension B
Mol ratio is 4.5~5.5:1:1；
4) the nano manganese phosphate lithium material and organic carbon source of preparation are dispersed in water, are granulated through atomization drying and obtain 3~8 μm
Spherical particle, the lithium manganese phosphate material of carbon coating is obtained under inert atmosphere through high-temperature calcination.
2. the preparation method of the lithium manganese phosphate material of carbon coating according to claim 1, it is characterised in that described step
3) heating response reacts 8~12h under the conditions of 150~180 DEG C in.
3. the preparation method of the lithium manganese phosphate material of carbon coating according to claim 1 or 2, it is characterised in that described
Phosphoric acid concentration is not less than 85wt%.
4. the preparation method of the lithium manganese phosphate material of carbon coating according to claim 3, it is characterised in that described step
1) in, the concentration of lithium acetate is 0.5~4.2mol/L in clear solution I, in clear solution II concentration of protochloride manganese for 0.2~
0.6mol/L。
5. the preparation method of the lithium manganese phosphate material of carbon coating according to claim 1 or 2, it is characterised in that described
Post processing refers to wash using deionized water and absolute ethyl alcohol in step 3), the centrifugation for being 8000rpm~12000rpm with rotating speed
Machine is centrifuged, and is dried at 60~100 DEG C and is obtained dry nano manganese phosphate lithium material.
6. the preparation method of the lithium manganese phosphate material of carbon coating according to claim 1 or 2, it is characterised in that described
The one kind of organic carbon source in glucose, sucrose, starch, polyvinylpyrrolidone, vitamin C, citric acid in step 4)
It is or a variety of.
7. the preparation method of the lithium manganese phosphate material of carbon coating according to claim 6, it is characterised in that described step
4) the feed end temperature of atomization drying is 190~240 DEG C in, and the temperature at collection material end is 100~130 DEG C, atomization rates 5
~20ml/min.
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| CN101609880A (en) * | 2009-07-16 | 2009-12-23 | 江苏富朗特新能源有限公司 | A kind of ferrousphosphate lithium material of carbon coated and preparation technology thereof |
| CN102427131A (en) * | 2011-09-09 | 2012-04-25 | 广州市香港科大霍英东研究院 | Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery |
| CN103258994A (en) * | 2013-05-06 | 2013-08-21 | 天津巴莫科技股份有限公司 | Positive material for lithium ion battery, preparation method of material, and lithium ion battery |
| CN105006569A (en) * | 2015-06-03 | 2015-10-28 | 浙江大学 | Nano-scale lithium manganese phosphate material and preparing method and application thereof |
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| CN101609880A (en) * | 2009-07-16 | 2009-12-23 | 江苏富朗特新能源有限公司 | A kind of ferrousphosphate lithium material of carbon coated and preparation technology thereof |
| CN102427131A (en) * | 2011-09-09 | 2012-04-25 | 广州市香港科大霍英东研究院 | Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery |
| CN103258994A (en) * | 2013-05-06 | 2013-08-21 | 天津巴莫科技股份有限公司 | Positive material for lithium ion battery, preparation method of material, and lithium ion battery |
| CN105006569A (en) * | 2015-06-03 | 2015-10-28 | 浙江大学 | Nano-scale lithium manganese phosphate material and preparing method and application thereof |
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